Principles of General Chemistry, 2nd ed. By M.

Silberberg
Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.

Chemical Periodicity

Lecture Goals
1. More About the Periodic Table
Periodic Properties of the Elements
2. Atomic Radii
3. Ionic Radii
4. Ionization Energy
5. Electron Affinity
6. Electronegativity

Periodic Table

More About the Periodic Table

Arranged by Dmitri Mendeliv, a Russian

Chemist
Establish a classification scheme of the
elements based on their electron
configurations.

Noble Gases

Column:
Row:

have completely filled electron shells

since they have similar electronic structures,

their chemical reactions are similar.

FAMILY or GROUP
PERIOD

Certain characteristics are shared by each

families & periods.

He
Ne
Ar
Kr
Xe
Rn

1s2
[He] 2s2 2p6
[Ne] 3s2 3p6
[Ar] 4s2 3d10 4p6
[Kr] 5s2 4d10 5p6
[Xe] 6s2 4f14 5d10 6p6

More About the Periodic Table

More About the Periodic Table

d-Transition Elements

Representative Elements

on periodic chart in B groups

are the elements in A

groups on periodic chart.

each metal has d

electrons.

will have their last

electron in an outer s or
p orbital
have fairly regular
variations in their
properties

ns (n-1)d configurations

make the transition from

metals to nonmetals
exhibit smaller variations
from row-to-row than the
representative elements
5

More About the Periodic Table

f - transition metals

The Periodic Table:

Metals, Nonmetals, and Metalloids
1869 - Mendeleev & Meyer

sometimes called inner

transition metals

The properties of the elements are periodic

functions of their atomic numbers.

have electrons in f
orbitals & are being
added two shells below
the valence shell
very slight variations of
properties from one
element to another.

The Periodic Table:

Metals, Nonmetals,
and Metalloids
Groups or families

The Periodic Table:

Metals, Nonmetals, and Metalloids
Period
Horizontal group of elements on periodic table
Transition from metals to nonmetals

Vertical group of elements

on periodic table
Similar chemical and
physical properties

Metals
Some chemical properties
1.
2.
3.
4.

Outer shells contain few electrons

Form cations by losing electrons
Form ionic compounds with nonmetals
Solid state characterized by metallic bonding

The Alkali Metals

Group IA metals:
Li, Na, K, Rb, Cs, Fr

example of a periodic trend

their reactions with water

The Alkaline Earth Metals

Non Metals

Group IIA metals

Be, Mg, Ca, Sr, Ba, Ra

Some chemical properties

1.
2.
3.
4.

Halogens
Group VIIA nonmetals
F, Cl, Br, I, At

Noble, Inert or Rare Gases

Group VIIIA nonmetals
He, Ne, Ar, Kr, Xe, Rn

Outer shells contain four or more electrons

Form anions by gaining electrons
Form ionic compounds with metals and covalent
compounds with other nonmetals
Form covalently bonded molecules; noble gases
are monatomic

Chalcogens
Group VIA nonmetals
O, S, Se, Te

The Periodic Table:

Metals, Nonmetals, and Metalloids
Metals are to the left
of stair step.
~ 80% of the elements

Best metals are on

the far left of the
table.

The Periodic Table:

Metals, Nonmetals, and Metalloids

The Periodic Table:

Metals, Nonmetals, and Metalloids

Non metals are to

the right of stair step.

Metalloids have one

side of the box on the
stair step.

~ 20% of the elements

Best metals are on

the far right of the
table.

Periodic Properties
of the Elements

The Periodic Table:

Metals, Nonmetals, and Metalloids

By definition, periodic is appearing or recurring

at regular intervals .

Periodic trends in metallic character

More Metallic
More
Metallic

to be discussed:
Atomic Radii
Ionic Radii
Ionization Energy
Electron Affinity
Electronegativity

Periodic
Chart

22

Atomic Radii
describes the relative sizes of atoms.
increase within a column going from the
top to the bottom of the periodic table
decrease within a row going from left to
right on the periodic table

23

Atomic
Radii

24

Atomic Radii

Atomic Radii

The reason the atomic radii decrease across

a period is due to shielding or screening
effect.
Effective nuclear charge, Zeff, experienced
by an electron is less than the actual
nuclear charge, Z.
The inner electrons block the nuclear
charges effect on the outer electrons.

Moving across a period, each element has an

increased nuclear charge and the electrons are
going into the same shell (2s and 2p or 3s and
3p, etc.).
Consequently, the outer electrons feel a
stronger effective nuclear charge.
For Li, Zeff ~ +1
For Be, Zeff ~ +2

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Atomic Radii

26

Ionic Radii

Arrange these elements based on their

atomic radii.

Cations (positive ions) are always smaller

than their respective neutral atoms.
Element

Se, S, O, Te
O < S < Se < Te
P, Cl, S, Si
Cl < S < P < Si
Ga, F, S, As
F < S < As < Ga

Na

Mg

Al

Atomic
Radius ()

1.86

1.60

1.43

Ion

Na+

Mg2+

Al3+

Ionic
Radius ()

1.16

0.85

0.68

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Ionic Radii

Ionic Radii
Anions (negative ions) are always larger
than their neutral atoms.

Cations (positive ions) are always smaller

than their respective neutral atoms.
Element
Atomic
Radius ()
Ion
Ionic
Radius ()

28

Li

Be

1.52

1.12

Atomic
Radius()

Li+

Be2+

Ion

0.90

0.59

Ionic
Radius()

Element

29

0.75

0.73

0.72

N3-

O2-

F1-

1.71

1.26

1.19

30

Ionic Radii

Ionic Radii
Cation (positive ions) radii decrease from left
to right across a period.
Increasing nuclear charge attracts the electrons
and decreases the radius.

Ion

Rb+

Sr2+

In3+

Ionic
Radii()

1.66

1.32

0.94

31

Ionic Radii

32

Ionic Radii

Anion (negative ions) radii decrease from left

to right across a period.
Increasing electron numbers in highly charged
ions cause the electrons to repel and increase the
ionic radius.

Ion

N3-

O2-

F1-

Ionic
Radii()

1.71

1.26

1.19

Arrange these elements based on their

ionic radii.
Ga, K, Ca
K1+ > Ca2+ > Ga3+
Cl, Se, Br, S
Cl1- < S2- < Br1- < Se2-

33

34

Ionization Energy

Ionization Energy

First ionization energy (IE1)

Second ionization energy (IE2)

The minimum amount of energy required to remove

the most loosely bound electron from an isolated
gaseous atom to form a 1+ ion.

The amount of energy required to remove the

second electron from a gaseous 1+ ion.

Symbolically:

Symbolically:

Atom(g) + energy ion+(g) + e-

ion+ + energy ion2+ + e-

Mg+ + 1451 kJ/mol Mg2+ + e-

Mg(g) + 738kJ/mol Mg+ + e-

Atoms can have 3rd (IE3), 4th (IE4), etc. ionization energies.
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36

Ionization Energy

Ionization Energy

Periodic trends for Ionization Energy:

Periodic trends for Ionization Energy:

1. IE1 generally decreases moving down a family.

1. IE2 > IE1

IE1 for Li > IE1 for Na, etc.

It always takes more energy to remove a second

electron from an ion than from a neutral atom.

2. IE1 generally increases moving from IA

elements to VIIIA elements.
Important exceptions at Be & Mg, N & P, etc. due to
filled and half-filled subshells.

37

First Ionization Energies

of Some Elements

38

Ionization Energy
Arrange these elements based on their
first ionization energies.
Sr, Be, Ca, Mg
Sr < Ca < Mg < Be
Al, Cl, Na, P
Na < Al < P < Cl
B, O, Be, N
B < Be < O < N
39

Ionization Energy

40

Ionization Energy
Group
and
element
IE1
(kJ/mol)

First, second, third, etc. ionization

energies exhibit periodicity as well.
Look at the following table of ionization
energies versus third row elements.
Notice that the energy increases
enormously when an electron is removed
from a completed electron shell.

41

IA
Na

IIA
Mg

IIIA
Al

IVA
Si

496

738

578

786

IE2
(kJ/mol)

4562

1451

1817

1577

IE3
(kJ/mol)

6912

7733

2745

3232

IE4
(kJ/mol)

9540

10,550

11,580

4356

42

Ionization Energy

Ionization Energy

The reason Na forms Na+ and not Na2+ is that

the energy difference between IE1 and IE2 is
so large.
Requires more than 9 times more energy to
remove the second electron than the first one.

The same trend is persistent throughout the

series.
Thus Mg forms Mg2+ and not Mg3+.
Al forms Al3+.

What charge ion would be expected for an

element that has these ionization energies?
IE1 (kJ/mol)
IE2 (kJ/mol)
IE3 (kJ/mol)

1680
3370
6050

IE4 (kJ/mol)
IE5 (kJ/mol)
IE6 (kJ/mol)

8410
11020
15160

IE7 (kJ/mol)
IE8 (kJ/mol)

17870
92040

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44

Electron Affinity

Electron Affinity

is the amount of energy absorbed

when an electron is added to an
isolated gaseous atom to form an ion
with a 1- charge.
Sign conventions for electron affinity.

is a measure of an atoms ability to form

negative ions.
Symbolically:

If electron affinity > 0 energy is absorbed.

If electron affinity < 0 energy is released.
atom(g) + e- + EA ion-(g)
45

Electron Affinity

46

Electron Affinity

Two examples of electron affinity values:

Mg(g) + e- + 231 kJ/mol Mg-(g)
EA = +231 kJ/mol

Br(g) + e- Br-(g) + 323 kJ/mol

EA = -323 kJ/mol

General periodic trend for electron affinity is

the values become more negative from left to right
across a period on the periodic chart.
the values become more negative from bottom to
top up a row on the periodic chart.

Measuring electron affinity values is a difficult

experiment.

47

48

Electron Affinity

Electron Affinity

49

Electron Affinity

50

Electronegativity

Arrange these elements based on their

electron affinities.
Al, Mg, Si, Na
Si < Al < Na < Mg

is a measure of the relative tendency of an

atom to attract electrons to itself when
chemically combined with another
element
is measured on the Pauling scale
Fluorine is the most electronegative element.
Cesium and francium are the least
electronegative elements.

51

Electronegativity

52

Electronegativity

For the representative elements,

electronegativities usually increase from left
to right across periods and decrease from top
to bottom within groups.

53

54

Electronegativity
Arrange these elements based on their
electronegativity.
Se, Ge, Br, As
Ge < As < Se < Br
Be, Mg, Ca, Ba
Ba < Ca < Mg < Be

If knowledge can create

Chemical
problems, then it is not through
ignorance that we can solve
Periodicity
them.
Isaac Asimov

questions?

55